Silver halide emulsion containing copolymer of glycidyl methacrylate and vinyl monomer as hardener

ABSTRACT

A PHOTOGRAPHIC LIGHT-SENSITIVE ELEMENT COMPRISING AT LEAST ONE GELATIN LAYER WHEREIN THE GELATIN LAYER CONTAINS AN AQUEOUS SOLUTION OR DISPERIOSN OF A COPOLYMER OF GLYCIDYL METHACRYLATE OR GLYCIDYL ACRYLATE, AND A VINYL MONOMER. THE COPOLYMER LENDS ENHANCED HARDENING PROPERTIES TO THE GELATIN.

3,623,878 SILVER HALIDE EMULSION CONTADIING C- POLYMER OF GLYCIDYL METHACRYLATE AND VDIYL MONOMER AS HARDENER Fumihiko Nishio, Nobuo Tsuji, Kinji Ohkubo, Kotaro Yamasue, and Tatsuya Tajima, Minami Ashigaramachi, Kanagawa, Japan, assignors to Fuji Photo Film Co., Ltd, Minami Ashigara-machi, Japan No Drawing. Filed Mar. 28, 1969, Ser. No. 811,627 Claims priority, application Japan, Mar. 28, 1968, 43/ 20,260 Int. Cl. G03c 1/30 U.S. Cl. 96-111 19 Claims ABSTRACT OF THE DISCLOSURE A photographic light-sensitive element comprising at least one gelatin layer wherein the gelatin layer contains an aqueous solution or dispersion of a copolymer of glycidyl methacrylate or glycidyl acrylate, and a vinyl monomer. The copolymer lends enhanced hardening properties to the gelatin.

BACKGROUND OF THE INVENTION Field of the invention The present invention relates to a photographic lightsensitive element, and more particularly to a hardening agent, that is, an agent for hardening gelatin, to be incorporated in a gelatin layer useful in photographic light-sensitive element.

Description of the prior art In the production of photographic light-sensitive elements, e.g., photographic light-sensitive films, gelatin is widely used as a binder component (a vehicle) for photographic layers such as a light-sensitive silver halide emulsion layer, an under-coating layer, a backing layer, a protective layer for silver halide emulsion layers, an antihalation layer, and the like. However, when a layer composed of gelatin is mechanically weak, the layer formed tends to be easily scratched by rubbing. Furthermore, when the .gelatin layer is swollen or weakened during photographic processings such as developing, fixing and water washing, the tendency for scratching, etc., is

severe.

On the other hand, a photographic light-sensitive element in which paper is employed as the support is, after processing (such as exposure, developing, fixing, and water washing), dried and glazed, often by means of a ferrotype glazing machine. In such a case, when the melting point of the gelatin which is used as the binder is much lower than the surface temperature of the glazing plate, the emulsion layer or protective layer composed of gelatin is melted off at the glazing plate, causing the phenomenon called ferrotype melting (the melting of the emulsion layer due to the heat of glazing machine). Moreover, when a printing paper is subjected to drying by a glazer while a gelatin layer faces the cloth-covered side of the glazing machine, the layer frequently becomes partially attached to the cloth.

The prior art, to overcome the aforesaid difficulties caused by mechanical weakness of the gelatin layer, has attempted to harden he gelatin by cross linking the side chains of the gelatin to each other using a material capable of cross linking the side chains of gelatin. This is nited States Patent 3,623,878 Patented Nov. 30, 1971 ice in the photographic 5 been employed inorganic compounds, such as chromium salts and aluminum salts, or organic compounds such as aldehydes, e.g., formaldehyde and others as mucochloric acid. However, such conventional hardening agents are deficient in that at the beginning (when a photographic layer such as a silver halide emulsion layer containing the hardening agent is applied to a support), the mechanical properties of the layer are not improved, and the hardening effect of the hardening agent does not sufficiently appear before a considerable period of time (about 30 days or more) has elapsed.

In order to provide sufficient mechanical strength to gelatin layers for use in light-sensitive elements within a short period of time (e.g., 1-2 days) after the application of these layers to a support, the amount of hardening agent in the gelatin layers has been increased, but in this case, the viscosity of the gelatin solution containing the silver halide to which the hardening agent has been added is increased considerably during the coating operation, and the the coating thickness becomes thicker when the coating operation occurs after increasing lapses of time. This makes the coating operation frequently very ditficult.

As disclosed in the specification of US. Pat. No. 2,376,005, it has been proposed to incorporate an aqueous dispersion of a polymer in a gelatino silver halide emulsion to improve the strength of the layer for use in a lightsensitive element. However, the action of these polymers as hardening agents is frequently insutficient, and some of the polymers decrease the transparency of the gelatin layer and thus haze the layer.

The present invention does provide an answer to the problems which have heretofore plagued the prior art in that an improved hardening agent and a photographic light-sensitive material utilizing an improved hardening agent is provided.

SUMMARY OF THE INVENTION The present invention provides an improved hardening agent and an improved photographic light-sensitive material utilizing the hardening agent. The hardening agent comprises a copolymer of glycidyl methacrylate or glycidyl acrylate and a vinyl monomer, and is in the form of an aqueous dispersion or solution in at least one gelatin layer occurring in the photographic light-sensitive element. The gelatin layer may be, inter alia, a gelatino silver halide emulsion layer, a protective layer, an antihalation layer, or a backing layer.

Preferred embodiments of the invention are described in the description of the preferred embodiments.

Thus, an object of the present invention is to provide a photographic light-sensitive element having at least one gelatin layer containing an improved hardening agent which is not accompanied by the aforesaid faults.

Another oobject of this invention is to provide an improved hardening agent for use in photographic lightsensitive elements.

DESCRIPTION OF THE PREFERRED EMBODIMENTS According to the present invention, there is provided a gelatino silver halide photographic light-sensitive element having a gelatin layer containing as a hardening agent an aqueous dispersion of a copolymer of glycidyl methacrylate or glycidyl acrylate and a vinyl compound. Glycidyl methacrylate or glycidyl acrylate, used as a ingredient of the copolymer of this invention, are represented by the following chemical formulae:

Glycidyl methacrylate:

The vinyl compound which is copolymerized with glycidyl methacrylate or glycidyl acrylate is a monomer capable of being substantially copolymerized with glycidyl methacrylate or glycidyl acrylate, causing no reaction with the glycidyl group during emulsion polymerization, thereby making emulsion polymerization possible. As examples of such vinyl monomers, there are alkyl acrylates, alkyl methacrylates, tit-substituted alkyl acrylates, acrylamide derivatives, methacrylamide derivatives, a-substituted acrylamide derivatives, vinyl esters, vinyl halides, vinylidene halides, vinyl oxazolidinone, vinylpyrrolidone, other N-vinylamides, vinylpyridine, styrene, styrene derivatives, butadiene, isoprene, acrylonitrile, methacrylonitrile, and the like.

The copolymer used as a hardening agent in the present invention can be obtained by the copolymerization of the aforesaid glycidyl methacrylate or glycidyl acrylate and the aforesaid vinyl compound. To obtain the copolymer as an aqueous dispersion, the monomers, i.e., glycidyl methacrylate or glycidyl acrylate and the vinyl compound abovementioned, are added to degassed distilled water in an amount of -60% by weight of the total system, suitable amounts of anionic surface active agents and water soluble polymerization initiators such as potassium persulfate are added to the system, and after adding, if necessary, additives for polymerization, the mixture is stirred vigorously for several hours at -90 C. By this procedure, the desired aqueous emulsified dispersion of the copolymer is obtained.

In the above case, however, when the proportion of glycidyl methacrylate or glycidyl acrylate is less than 10 mole percent, the hardening agent thus prepared shows an insufficient hardening action. On the other hand, when the proportion thereof is higher than 90 mole percent, the copolymer tends to form aggregates with itself when the copolymer is added to a solution of gelatin, whereby the layer thus formed tends to become opaque. Therefore, it is desirable that the copolymerization ratio of glycidyl methacrylate or glycidyl acrylate to the vinyl compound comonomer be from 1/9 to 9/1 (mole ratio).

The aqueous dispersion of the copolymer in this invention may be prepared, as mentioned above, by subjecting the monomeric ingredients to emulsion polymerization onic surface active agents, there are lauryl sulfate alcohol, sodium alkylbenzene sulfonate, sodium l3-(p-nonylphe'noxy-5,8,l1-trioxatridecane-l-sulfate), and the like.

However, when the emulsion polymerization is conducted using a sucrose mono-ester of lauric acid which is a nonionic surface active agent) or cetyl chloride, trimethyl ammonium, etc., which are cationic surface active agents, there is one fault, i.e., when the copolymer is added to a solution of gelatin as a hardening agent, the copolymer tends to be coagulated due to poor compatibility with the gelatin solution.

Furthermore, if the particle size of the copolymer in the aqueous dispersion thereof used in this invention is too large, the compatibility thereof with gelatin is poor. The particle size, as is known by those skilled in the art, is controlled by the conditions for emulsion polymerization. That is, the particle size can be controlled by adjusting the reaction conditions such as the amount of a surface active agent as the dispersion agent, the stirring conditions, the reaction time, the reaction temperature, and the like. The particle size employed in this invention is usually from 0.01 to 1 micron preferably from 0.05 to 0.3 micron.

The following examples show several embodiments for preparing the aqueous dispersions of the copolymers used in this invention as a hardening agent.

PREPARATION 1 A glass-lined close-type reaction vessel having temperature control means, a stirrer, a reflux condenser, heating means, and a gas inlet was purged with nitrogen gas. Into the reaction vessel were charged 800 parts by weight of degassed distilled water, 120 parts by weight of glycidyl methacrylate which had been purified by distillation to remove any polymerization inhibitor and parts by weight of butyl methacrylate (the mole ratio of glycidyl methacrylate to butyl methacrylate was 60/40). After adding further 50 parts by weight of sodium dodecylbenzene sulfonate as a dispersing agent, the reaction mixture was stirred vigorously by means of a stirrer at 500- 800 rpm. to be emulsified. Thereafter, 0.15 part of ammonium persulfate and 0.05 part by weight of sodium bisulfite as a polymerization initiator were added, and the system was maintained at l00 C. with stirring. The reaction was continued for 6 hours, the polymerization being finished completely. The particle size of the solid polymer in the aqueous dispersion of the glycidyl methacrylate copolymer thus prepared was confirmed to be about 0.1-0.3 micron by electron microscope measurements.

PREPARATION 2 The same procedure as in Example 1 was repeated using the same reaction vessel as in the example but 754 parts by weight of distilled water, 80 parts by weight of glycidyl methacrylate, parts of butyl acrylate, (mole ratio of glycidyl methacylate to butyl acrylate being 40/60), 9.3 parts by weight of as a dispersing agent, and 0.5 part of potassium persulfate as a polymerization initiator were added. The particle size of the solid polymer in the aqueous dispersion of the glycidyl methacrylate/butyl acrylate copolymer thus obtained was confirmed to be 0.10.3 micron.

PREPARATION 3 The same procedure as in Example 1 was repeated using the same reaction vessel as in the example but parts by weight of glycidyl acrylate and 70 parts by weight of ethyl acrylate instead of glycidyl methacrylate and butyl methacrylate were added (the other components being the same) to provide an aqueous emulsified dispersion of a copolymer of substantially the same size.

PREPARATION 4 The same procedure as in Example 1 was repeated using the same reaction vessel as in the example and 80 parts by weight of glycidyl acrylate and 120 parts by weight of styrene were used to replace the monomers (other conditions being equal) to provide an aqueous emulsified dispersion of a copolymer of substantially the same size.

PREPARATION 5 The same procedure as in Example 1 was repeated by using the same reaction vessel, etc. as in the example, but 120 parts by weight of glycidyl methacrylate and 80 parts by weight of vinyl acetate were used as the monomers to provide an aqueous emulsified dispersion of a copolymer of substantially the same size.

IPREPARATION 6 The same procedure as in Example I was repeated by using the same reaction vessel as in the example, but the,

following components were changed: 80 parts by weight of glycidyl methacrylate and 120 parts by weight of acrylonitrile were used as the monomers and 9.3 parts by weight of sodium lauryl sulfate as the dispersing agent. Other conditions were equal and there was thereby provided an aqueous emulsified dispersion of a copolymer of substantially the same size.

The aqueous dispersion of copolymers prepared above may be used alone or as a mixture of two or more kinds thereof in this invention. Moreover, the dispersion may be used together with other aqueous emulsified dispersion of polymers having no glycidyl group, and this case is sometimes more effective for some purposes.

The weight ratio of the copolymer of the aqueous dispersion thereof (the weight of monomer used for preparing the copolymer) to the gelatin is desirably from 0.05/1 to 1/ 1. If the ratio is less than 0.05/1, the effect of the aqueous dispersion of copolymer is too weak, and if it is higher than l/l, the layer is hardened too much, which delays the developing procedure.

The aqueous dispersion of copolymer of this invention may be incorporated in a gelatino silver halide emulsion layer as well as into other gelatin-containing layers such as a protective layer, an antihalation layer, a backing layer and the like.

When a gelatin-containing solution or dispersion having incorporated therein the aqueous dispersion of the copolymer of glycidyl methacrylate or glycidyl acrylate and the vinyl compound is applied to a support, a layer having a sufiiciently high transparency as well as a very high hardness and excellent wear resistance can be obtained in a short period of time after coating and drying. Also, the gelatin-containing solution or dispersion can be utilized for preparing photographic printing paper, ferrotype melting of printing paper during glazing by a glazer can be prevented. Forthermore, aqueous dispersions of copolymers in accordance with the present invention provide many advantages, such as that when the dispersion is incorporated in a gelatin solution in an amount sufficient to show an adequate hardening effect, the viscosity change when the solution is stored for a long period of time is lessened.

The invention will now be further explained by the following examples from a final coating aspect.

Example 1 To 1 kg. of a gelatino silver chlorobromide emulsion containing 7.5% by weight gelatin and 2.5% by weight silver chlorobromide was added ml. (no addition; control example), 50 ml., 100 ml., 150 ml. or 200 ml. of the aqueous dispersion of the copolymer of glycidyl methacrylate and butyl methacrylate prepared by the procedure as in Preparation 1 described above to provide five kinds of photographic light-sensitive emulsions. Each of the emulsions thus prepared was applied to a photographic baryta-coated paper so that the amount of silver per unit area of the emulsion layer was the same in each case. The layer was then dried.

These samples were allowed to stand for three days at room temperature after drying and further allowed to stand for 24 hours at a temperature of 50 C. and at a relative humidity of 90%. Thereafter, the melting point of the emulsion layer was measured. The melting point was obtained by immersing the sample in an aqueous one normal solution of oxalic acid, and increasing the temperature of the solution at a rate of 1 C./min. with measuring the temperature at which the emulsion layer was melted and stripped from the support. The results are shown in the following table.

Sample 6 7 8 9 Amount of aq. 6% Formalin solution added ml. 10 25 40 65 M.P. (after 3 days) C.) 42 48 54 62 M.P. (after 24 hours at R The above results show that the emulsion layer having incorporated therein the aqueous dispersion of the copolymer of glycidyl methacrylate and butyl methacrylate had a very high melting point, even after being allowed to stand for three days after drying. Although the melting point of the emulsion layer was increased when the amount of Formalin solution was increased, the hardness of the Formalin-containing layer when the layer was allowed to stand for three days after drying was insufficient. More specifically, the melting point of the formaldehyde-containing layer was suddenly increased when the layer was allowed to stand for 24 hours at a temperature of 50 C. and a relative humidity of 90% As the next step, 150 ml. of the aqueous dispersion of the copolymer of glycidyl methacrylate and butyl methacrylate was added to 1 kg. of the photographic emulsion mentioned above to provide a sample in accordance with this invention. 40 ml. of an aqueous 6% Formalin solution was also added to 1 kg. of the photographic emulsion to provide a comparative sample. The viscosity change of each of the samples was observed by measuring the viscosity of the emulsion after 0 hours, 2 hours, and 4 hours, while maintaining the sample at 35 C. (The viscosity was shown by the specific viscosity at 35 C.) The results are shown in the following table.

Viscosity after As shown above, when the proportion of an aqueous solution of Formalin was increased to thereby increase the melting point of the layer in a short period of time after coating and drying, the viscosity of the gelatino silver halide emulsion containing formaldehyde was greatly increased as time passed, and the thickness of the emulsion layer changed. Further, and perhaps most importantly, the coating became impossible after four hours.

On the other hand, when the aqueous dispersion of the copolymer of glycidyl methacrylate and butyl methacrylate of this invention was added to a gelatino silver halide emulsion and the resulting emulsion was applied to a support to form a layer, the melting point of the layer became very high in a short period of time after coating and drying, the viscosity increase was comparatively less and the deviation of the thickness of layer during coating was in a controllable range.

Example 2 Into '1 kg. of a coating composition for use as an antihalation layer consisting of an aqueous 6% by weight gelatin solution containing a standard antihalation dye, there was incorporated (separate 1 kg. base for each):

(1) ml. of the aqueous dispersion of the copolymer of glycidyl-methacrylate and butyl acrylate (4:6 mole ratio) prepared in Preparation 2 above;

(2) 100 ml. of the aqueous dispersion of a homopolymer of glycidyl methacrylate prepared by the same procedure as in Preparation 2 using only glycidyl methacrylate instead of glycidyl methacrylate and butyl acrylate;

(3) 100 ml. of the aqueous dispersion of a homopolymer of butyl acrylate prepared by the same procedure as in Preparation 2 using only butyl acrylate instead of glycidyl methacrylate and butyl acrylate;

(4) 80 ml. of an aqueous 2% mucochloric acid (a conventional organic hardening agent).

The resulting mixtures were applied to a cellulose triacetate film having a gelatin under coating so that the dry thickness of the layer was 9.0105 micron. After drying the four kinds of samples thus prepared, they were allowed to stand for days at room temperature, and the melting point of the layers was measured as in Example 1. To test the strength of the layer of the samples during development, each sample was developed for three minutes in a commercial developer, and the surface of the layer of the sample immersed in the developer was scratched with a loaded metallic stylus. The minimum weight of the loaded metallic stylus capable of scratching the surface (scratch hardness) was measured.

After development, the sample was processed for two minutes in a conventional fixing solution and the scratch hardness of the surface of the layer was again measured by means of a loaded metallic stylus. Further, after fixing, the sample was washed with flowing water for minutes and the scratch hardness of the surface of the film was again measured. After mixing and water-washing, the permeability of the layer was also measured. The results are shown in the following table.

Preparation 3 (6:4 mole ratio). After stirring thoroughly, the resulting mixture was applied to a photographic baryta-coated paper having a weight of 150 g./m. so that the same amount of silver was applied to the paper throughout this series of tests. After drying, the samples were allowed to stand at room temperature for four days, 15 days, days, and days, respectively. Other samples (same composition) were allowed to stand for 24 hours at a temperature of C. and a relative humidity of Each of these samples thus stored was subjected to the following processings: development, stopping, fixing, water washing and then drying by a glazer at C.

One kg. of the aforesaid gelatino silver halide emulsion was also mixed with: (2) 10 ml. of an aqueous 5% chromium alum solution and 30 ml. of an aqueous 6% Formalin solution; (3) 15 ml. of an aqueous 5% chromium alum solution and 65 ml. of an aqueous 6% Formalin solution; or (4) 150 ml. of an aqueous dispersion of a homopolymer of ethylacrylate. Each of the resulting mixtures was applied to a support and dried, and thereafter each of the samples thus prepared was subjected to the above-described processings and drying by a glazer.

For the samples thus prepared, the condition of a sample where the surface of the layer after drying by Sample Melting point C.)

atter- Scratch strength (g.)

(1) ml. of copolymer of glycidyl methacrylate and butyl aerylate (2) 100 ml. of homopolymer of glycidyl methacrylate (3) 100 ml. of homopolymer of butyl aerylate (4) 80 ml. of mucochloric acid (2%) From these results, it was confirmed that the gelatin film containing the aqueous dispersion of the copolymer of glycidyl methacrylate and butyl acrylate had a higher melting point than the gelatin layer containing the aqueous dispersion of each of the aforesaid homopolymers. Also, the scratch hardness of the former layer was higher than those of the gelatin layers containing the aqueous dispersion of the homopolymers of glycidyl methacrylate or butyl acrylate, or an aqueous solution of mucochloric acid.

Moreover, in the case of employing the aqueous dispersion of this invention, no haze formation was observed, and the transparency of the layer was not lowered.

Example 3 To 1 kg. of a gelatino silver halide emulsion containing 10.2% by weight gelatin and 3.5% by weight silver chloroiodobromide consisting of 48 mole percent silver chloride, 50 mole percent silver bromide and 2 mole percent silver iodide, there was added ml. of the aqueous dispersion of the copolymer of glycidyl acrylate and ethyl acrylate prepared by the procedure as in 24 hrs. at 90% Forum- R.H. and Develop Water tion of 10 days 50 0. ing, Fixing washing haze 72 82 50 65 60 None. 42 72 38 52 46 Hazy. 40 58 45 6O 50 None. 46 78 40 55 47 None.

After Alter After After After 24 hrs. 4 15 25 40 at 90% R.H. Addition compound days days days days and 50 C.

(1) 150ml. of copolymer A A A A A of glycidyl methacrylate and ethyl aerylate. (2) 10 ml. of an aqueous D C B B A 50% chromium alum sol. and 30 ml. of an aqueous 6% Formalin solution. (3) 15 ml. of an aqueous C B B A A 5% chromium alum sol. and 65 ml. of an aqueous 6% Formalin solution. (4) 150 ml. of aqueous D D D D C dispersion of copolymer of ethylaerylate.

As is clear from these results, the layer prepared using the aqueous dispersion of the copolymer of glycidyl methacrylate and ethyl acrylate gave no ferrotype melting even within a short period of time after coating and drying. Such a result could not be obtained by the layers prepared by using chromium alum and increased amounts of Formalin respectively. Moreover, as in Example I, the

emulsion of experiment 1) showed a lowered viscosity increase with lapse of time. On the other hand, in the case of experiment (3), the viscosity greatly increased with lapse of time, and coating became impossible after 4 hours.

Example 4 A gelatine silver halide emulsion containing 8.2 percent by weight of gelatin and 2.7 percent by weight of silver chlorobromide (70 mole percent silver bromide and 30 mole percent silver chloride) was applied to a photographic baryta-coated paper of 240 g./sq. In. at a dry thickness of 12 microns. On the layer thus prepared there was applied as a protective layer a mixture of one liter of a solution containing 2.2 percent by weight gelatin and: (l) 200 ml. of an aqueous dispersion of the copolymer of glycidyl acrylate and styrene (4:6 mole ratio) prepared by Preparation 4 described above; (2) 30 ml. of an aqueous 6 percent Formalin solution; or (3) 70 ml. of an aqueous 6 percent Formalin solution all at a dry thickness of about 0.8 microns. The layers were dried.

These three samples were allowed to stand at room temperature for four days, 15 days, 25 days, or 40 days, and thereafter the melting point of thus formed layer was measured as in Example 1. Also each of the samples was developed, stopped, fixed, water Washed and subjected to drying by a glazer at a temperature of 95 C. With respect to the samples dried, the extent of the attaching of naps to the emulsion layer was designated by the symbols A, B, C, and D, wherein the symbol A represents the smallest amount of nap. The value in the parenthesis is the melting point of the emulsion layer.

After After After After Sample 4 days 15 days 25 days 40 days 1 A (72 C.) A (73 C.) A (75 C.) A (76 C.) 2 C (49 C.) C (58 C.) B (69 C.) B (70 C.) 3 C (55 0.) B (62 C.) A (70 C.) A (73 C.)

To 1 kg. of a gelatino silver chlorobromide emulsion containing 7.5 percent by weight gelatin and 2.5 percent by weight silver chlorobromide, there was added ml., 50 ml., 100 ml., 150 ml., 200 ml. of the aqueous dispersion of the copolymer of glycidyl methacrylate and vinyl acetate prepared by the procedure as in Preparation to provide five kinds of photographic light-sensitive emulsions. Each of the emulsions thus prepared was applied to a photographic baryta-coated paper as in Example 1. The melting point of the emulsion layer was measured as in Example 1. The results are shown in the following table;

Sample 1 2 3 4 5 Amount of the copolymer, (ml.) O 50 100 150 200 MR after 3 days 0.). 58 68 76 82 M.P. after 24 hours at 90% RH. and 50 0.

1 Above 35.

Example 1, the viscosity increase of the emulsion containing the aqueous dispersion was comparatively low.

Example 6 Into 1 kg. of a coating composition for use as an antihalation layer consisting of an aqueous 6 percent by weight gelatin solution containing a standard antihalation dye as in Example 2, there was incorporated each of (1) 100 ml. of the aqueous dispersion of the copolymer of glycidyl methacrylate and acrylonitrile (4:6 mole ratio) prepared in Preparation 6.

(2) 100 ml. of the aqueous dispersion of a homopolymer of glycidyl methacrylate as in Example 2.

(3) 100 ml. of the aqueous dispersion of a homopolymer of acrylonitrile prepared by the exact procedure of Preparation 6, except using only acrylonitrile instead of glycidyl methacrylate and acrylonitrile.

(4) ml. of an aqueous 2 percent of mucochloric acid (a conventional organic hardening agent).

The resulting mixture was applied to a cellulose triacetate film having a gelatin under coating as in Example 2.

The melting point and the scratch strength of the layers were measured as in Example 2. The results are shown in the following table;

From the above results, it was confirmed that the gelatin film prepared by the aqueous dispersion of the copolymer of glycidyl methacrylate and acrylonitrile had a higher melting point than the other gelatin layer, and the scratch hardness of the former layer was higher than the gelatin layer prepared with the aqueous dispersion of each of the aforesaid homopolymer.

Example 7 The procedure of Example 1 was repeated except that the aqueous dispersion of the copolymer of glycidyl methacrylate and vinylidene chloride was employed instead of the aqueous dispersion of the copolymer of glycidyl methacrylate and butyl methacrylate. The emulsion layer having incorporated therein the aqueous dispersion of the copolymer had a very high melting point even after being allowed to stand for three days after drying.

All other conditions were the same as in Example 1.

To further define the substantially polymerized resins of the present invention, the following illustrative group is provided: alkyl in alkyl acrylate, alkyl methacrylate and alpha-substituted alkyl acrylate, having 1-8 carbon atoms, respectively, the alpha-substituted group is CL or -CN; acryl amide derivatives such as acrylamide, N,N-dimethyl acrylamide, N,N-diethyl acrylamide, N- methyl acrylamide, N-ethyl acrylamide, acryloyl morpholine; methacrylamide derivatives useful are those such as methacrylamide, N,N-dimethyl methacrylamide, N,N-diethyl methacrylamide, N-methyl methacrylamide, N- ethyl methacrylamide, methacryloyl morpholine; alphasubstituted acryl amide groups useful are CL, CN;

the other chemical structures are the same as those for the acrylamide derivatives; vinylesters useful are vinyl acetate, vinyl propionate, vinyl butylate; a useful vinyl halide is one as vinyl chloride; a useful vinylidene halide is one such as vinylidene chloride; other N-vinylamide utilizable are those such as N-methyl-N-vinyl acetoamide, N-methyl-N-vinyl formamide, N-vinyl caprolactam; styrene derivatives utilized are those such as alphamethyl styrene.

Further, with reference to the water utilized, it is necessary that the water he degassed, but not necessary that the water be distilled in all instances, so long as impurities which affect the basic reaction are not present.

Further, the surface activation utilized, is much preferably in the range 01-20 percent by weight, based on the total weight of monomer.

To further define the initiator, this is most preferably utilized within the range 0.01-l percent by weight based on the total weight of monomer.

Although time is substantially not critical with reference to the present invention, a most preferred reaction time is within the range 38 hours.

To further define how polymerization conditions will affect the size of the final particles, generally the size of the particles will become smaller as the amount of surface active agent utilized is increased. However, the size of the particles is generally not affected by the initiator material utilized, or the reaction time.

The developer referred to in the prior part of the specification comprises 500 cc. hot water, 30 grams anhydrous sodium sulfite, 7.5 grams p-formaldehyde, 22 grams sodium bisulfite, 7.5 grams boric acid, 22.5 grams hydroquinone, 1.6 grams potassium bromide, and water to make 1 liter. The fixer utilized in the heretofore provided portion of the specification comprises: first solution-hot water at 50 C. (600 cc.), 300 grams of hypo; second solutionhot water at 50 C. (200 cc.), grams of anhydrous sodium sulfite, 12 cc. of glacial acetic acid, grams of potassium alum and 12 grams of sodium metaborate. Generally, the first and second solutions are mixed together and water is added to make one liter. This results in a final fixer.

With reference to the developer and fixer described above, it will be appreciated by one skilled in the art that equivalent materials may be utilized, as the functioning of these materials is extremely well known in the art.

Finally, with reference to the inter-blending of a second polymer with a polymer of this invention, it should be realized that the other polymer can comprise 10- 90 percent by weight of the total polymer mixture. Obviously, this will depend upon the exact contemplated final use for the photographic light-sensitive element.

What is claimed is:

1. A photographic silver halide light-sensitive element comprising a support and at least one gelatin layer containing an aqueous solution of a copolymer of glycidyl methacrylate or glycidyl acrylate, and a vinyl monomer, capable of being substantially copolymerized with glycidyl methacrylate or glycidyl acrylate, causing no reaction with the glycidyl group during emulsion polymerization.

2. -A photographic light-sensitive element according to claim 1, wherein said vinyl monomer is selected from the group consisting of alkyl acrylate, alkyl methacrylate, alpha-chloro or alpha-cyano alkyl acrylate, the alkyl groups of said monomers each having from 1 to 8 carbon atoms, acrylamide, N,N-dimethyl acrylamide, N,N-diethyl acrylamide, N-methyl acrylamide, N-ethyl acrylamide, acryloyl morpholine, methacrylamide, N,N-dimethyl methacrylamide, N,N-diethyl methacrylamide, N- methyl methacrylamide, N-ethyl methacrylamide, methacryloyl morpholine, alpha-chloro or alpha-cyano acrylamide, vinyl acetate, vinyl propionate, vinyl butylate, vinyl halide, vinylidene halide, N-vinylamide, vinyl pyri- 12 dine, styrene, alpha-methyl styrene, butadiene, isoprene, acrylonitrile or methacrylonitrile.

3. A photographic light-sensitive element according to claim 1, wherein the ratio of the weight of the polymer in an aqueous dispersion to the weight of gelatin in an aqueous dispersion of from about 0.05:1 to about 1:1.

4. A photographic light-sensitive element according to claim 1, wherein the aqueous dispersion of a copolymer is prepared by the emulsion polymerization of monomers dispersed in water by an anionic surface active agent.

5. A photographic light-sensitive element according to claim 1, wherein said copolymers are particulate and have a diameter of from about 0.01 micron to about 1 micron.

6. A photographic light-sensitive element according to claim 1, wherein said gelatin layer is a gelatino silver halide emulsion layer 7. A photographic light-sensitive element according to claim 1, wherein said gelatin layer is a protective layer.

8. A photographic light-sensitive element according to claim 1, wherein said gelatin layer is an antlhalation layer.

9. A photographic light-sensitive element according to claim 1, wherein said gelatin layer is a backing layer.

10. -A photographic light-sensitive element according to claim 1, wherein said aqueous dispersion contains a copolymer consisting of from about 10-90 mole percent of a member from the group consisting of glycidyl methacrylate and glycidyl acrylate and from about 10 mole percent of a vinyl monomer.

11. A photographic light-sensitive element according to claim 10, wherein said vinyl monomer is selected from the group consisting of alkyl acrylate, alkyl methacrylate, alpha-chloro or alpha-cyano alkyl acrylate, the alkyl groups of said monomers each having 1 to 8 carbon atoms, acrylamide, N,N-dimethyl acrylamide, N,N-diethyl acrylamide, N-methyl acrylamide, N-ethyl acrylamide, acryloyl morpholine, methacrylamide, N,N-dimethyl methacrylamide, N,N-diethyl methacrylamide, N- methyl methacrylamide, N-ethyl methacrylamide, methacryloyl morpholine, alpha-chloro or alpha-cyano acryl amide, vinyl acetate, vinyl propionate, vinyl butylate vinyl halide, vinylidene halide, N-vinylamide, vinyl pyridine, styrene, alpha-methyl styrene, butadiene, isoprene, acrylonitrile or methacrylonitrile.

12. A photographic light-sensitive element according to claim 10, wherein the ratio of the weight of the polymer in an aqueous dispersion to the weight of gelatin in an aqueous dispersion of from about 0.05:1 to about 1:1.

13. A photographic light-sensitive element according to claim 10, wherein the aqueous dispersion of a copolymer is prepared by the emulsion polymerization of monomers dispersed in water by an anionic surface act1ve agent.

14. A photographic light-sensitive element according to claim 10, wherein said copolymers are particulate and have a diameter of from about 0.01 micron to about 1 micron.

15. A photographic light-sensitive element according to claim 1, wherein said aqueous solution is an aqueous dispersion.

16. A photographic light-sensitive element according to claim 15, wherein said aqueous dispersion is carried out through the employment of an anionic surface active agent.

17. A photographic light-sensitive element according to claim 16, wherein said anionic surface active agent is a member selected from the group consisting of lauryl sulfate alcohol, sodium alkylbenzene sulfonate, and sodium 13 (p nonylphenoxy 5,8,11 trioxatridecane 1- sulfate).

18. A photographic light-sensitive element according to claim 5, wherein said copolymers are particulate and have a diameter of from about 0.05 to about 0.3 micron.

19. A photographic light-sensitive element according 14 to claim 14, wherein said copolymers are particulate and 3,440,200 4/1969 Lindemann 260-8 have a diameter of from about 0.05 to about 0.3 micron. 3,448,089 6/ 1969 Celeste 96-88 References Cited NORMAN G. TORCHIN, Primary Examiner UNITED STATES PATENTS 5 W H. LOUIE, JR., Assistant Examiner 3,088,791 5/1963 Cline et a1. 260-8 X I 3,337,288 8/1967 Horiguchi et a1. 8-4 2 0 1 3,429,839 2/1969 Franco 260-8 6 17 

